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α-Bromo ketones, -esters and -nitriles react with chromium dichloride and ketones in a Barbier-type reaction to yield the kinetic crossed aldol products with one or two new quarternary centers. The reaction does not require special activation of the reagent, proceeds at room temperature and is suitable for microscale preparations. Crotonates react highly regioselective to yield α-products. The influence of solvents is discussed.
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(Diphenylmethylene)amine [benzophenone imine, DPMA-H] cleanly reacts with a variety of α,β-unsaturated esters, nitriles, ketones, and aldehydes 1a-q to give Michael type adducts 2a-q, generally, in respectable to excellent yields. Sterically congested and donor-substituted Michael acceptors do not react. The β-amino-substituted products can be further transformed in their protected form, or selectively deprotected under mild conditions, e.g. by catalytic hydrogenation.